Azo dyestuffs containing a ureido group



United States Patent Claims. 61. 260-195) ABSTRACT OF THE DISCLOSURE Azo-dyestuffs having the general formula /R RH IFOOMU wherein D represents a radical of a diazo component, R represents hydrogen or lower alkyl, n stands for l or 2 and Z represents a reactive group, and complex metal compounds of the aforesaid azo-dyestuffs wherein the radical D contains a substituent capable of being metallized in ortho-position to the azo-linkage useful in dyeing cellulose textiles with high tinctorial strength, purity of shade, good light fastness and resistance to Washing.

The present invention relates to new valuable azo dyestuffs and their metal complex compounds as well as to a process for preparing them; in particular, the invention provides azo dyestuffs which in their metal-free and acid form correspond to the following formula wherein D represents the radical of a diazo component which may contain additional substituents, in particular groups imparting solubility in water and, if desired, azo groups, R represents a hydrogen atom or an alkyl radical, n stands for 1 or 2, Z represents a group of one of the formulae and X represents an inorganic or organic radical which may be split off by an alkaline agent.

The hitherto unknown dyestuffs of Formula 1 can be prepared by known methods and may be converted, if desired, into their metal complex compounds likewise by known methods, provided the metal-free dyestuffs obice tained in this manner contain in ortho-position to the azo bridge a hydrogen atom or a substituent capable of forming metal complexes or of being converted. into a substituent of this kind.

As radical D of a diazo component which participates in the formation of the azo dyestuffs of the general Formula l obtainable according to the process of the present invention there may be mentioned, for example, a radical of the benzene, naphthalene, azobenzene, azonaphthalene, benzene-azonaphthalene, diphenyl, diphenylamine, pyrene, dehydrothiotoluidine or stilbene series.

The solubilizing groups which may be contained in said radical D of the diazo component are in the first place strongly acid groups imparting solubility in water such, for example,.as sulfonic acid or carboxylic acid groups, moreover low-molecular alkylsulfonyl groups as well as sulfonic acid amide groups or carboxylic acid amide groups. In addition, the radical D may contain further substituents which are usually present in. azo dyestuffs, for instance halogen atoms such as chlorine or bromine atoms, lower alkyl, lower alkoxy, acyl, acylamino, arylamino, hydroxy, nitro, cyano and trifluoromethyl groups as well as heterocyclic radicals, These groups may be linked in any position to the diazo component and may be distributed on the annulated rings.

As inorganic or organic radicals X which are split off by the action of alkaline agents there may be mentioned for example the following: halogen atoms such as a chlorine or bromine atom, an alkyl-sulfonic acid ester group or arylsulfonic acid ester group, moreover :acyloxy groups such as an acetoxy group, furthermore a sulfuric acid or thiosulfuric acid ester group as well as a phenoXy group or a dialkylamino group such, for example, as a dimethylor diethylamino group.

The preparation of the new metal-free azo dyestuffs of the general Formula 1 by coupling is advantageously carried out by treating the diazonium compound of an aromatic amine with a coupling component of the general formula (S0 11) ii in which R, Z and n have the meanings given above.

The coupling of the coupling components of Formula 4 with diazotized amines according to the process of the invention can be carried out by known methods in particular under weakly acid, neutral or weakly alkaline conditions. Especially when coupling in a weakly alkaline range it is advisable to operate at the lowest temperature possiblepreferably below 40 C.--in order to avoid undesirable side reactions which may cause, in particular, the loss of substituent X or the addition of water to the double linkage of the vinylsulfonyl group.

The above-mentioned diazonium compounds of primary aromatic amines which are used as starting substances in the process of the present invention can be obtained from the corresponding amines by known methods, for example by treatment with sodium nitrite in the presence of mineral acids, in particular in the presence of hydrochloric acid. The diazotization may likewise be effected by means of nitrosylsulfuric acid or in the presence of a-naphthalenesulfonic acid.

The following amines may serve as examples of diazotizable amines suitable for use in the process of the present invention:

l-aminobenzene,

l-aminobenzene-Z-sulfonic acid, 1-amino-benzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid, 1-aminobenzene-2,S-disulfonic acid, l-amino-4-chlorobenzene-2-sulfonic acid, l-amino-4-methyl-5-chlorobenzene-Z-sulfonic acid, l-amino-4-methylbenzene-2-sulfonic acid, l-amino-3-trifluoromethylbenZene-6-sulfonic acid, l-amino-3,4-dichlorobenzene-6-sulfonic acid, l-amino-4-methoxy-benzene-6-sulfonic acid, l-amino-3-methoxybenzene-6-sulfonic acid, 1-amino-3-methylbenzene-4-sulfonic acid,

moreover, ortho, metaand para-toluidine, ortho-anisidine, chloroand nitroaniline,

acid, acid, acid and acid, acid, acid, acid and as well as primary aromatic amines containing azo groups, for instance 4-amino-azobenzene-(1,1')-2,4-disulfonic acid.

If conversion of the metal-free azo dyestuffs obtained according to the process of the invention into their metal complex compounds is desired the following diazotizable amines may be used for example:

2-amin0benzene-l-carboxylic acid-4-sulfonic acid, Z-aminobenzene-l-carboxylic acid-S-sulfonic acid, Z-ZIIIliIlObCIlZfiIlfi-I-CQIbOXYiiC acid, 'nitroaminobenzene-carboxylic acids or aminohydroxybenzenes such as 4-methyl-, 4-chloroor 4-nitro-2-arnino-l-hydroxybenzene, 6-acetylamino-, 6-chloroor 6-nitro-2-amino-lhydroxybenzene-4-sulfonic acid, Z-amino-l-hydroxybenzene-4-sulfonic acid, Z-amino-l-hydroxybenzene--sulfonic acid, 4-nitro-6-acetylamino-2-amino-l-hydroxybenzene, 4-nitro-6-chloro-2-amino-l-hydroxybenzene, 4-chloroor 4-nitro-2-amino-l-hydroxybenzene-6- sulfonic acid, 4,6-dinitroor 4,6-dichloro-2-amino-l-hydroxybenzene, Z-amino-l-hydroxybenzene-4-sulfonic acid amide or Z-amino-l-hydroxybenzene-5-sulfonic acid amide and 3- n y r xy cnz ne-l-carbc ylic acid-S-suItQnic acid.

The above-mentioned coupling components of the general Formula 4 which may be used for the coupling, if desired in the form of their alkali metal salts, can be prepared in simple manner by reacting naphthalene derivatives of the general formula which contain an amino group capable of being acylated, with isocyanates or carbamic acid derivatives of the general formulae wherein R, Z and n are defined as above.

The isocyanates of Formula 6 and the carbamic acid derivatives of Formula 7 are new compounds which can be obtained from the corresponding arylamines, for instance by reaction of the amino group with phosgen or by condensation with chloroformic acid phenylester.

Among the naphthalene derivatives of Formula 5 which are suitable for use in the process of the invention there may be mentioned, for example l-amino-8-hydroxy-naphthalene-3-sulfonic acid,

l-amino-8-hydroxynaphthalene-4-sulfonic acid,

l-amino-8-hydroxynaphthalene-6-sulfonic acid,

l-amino-S-hydroxynaphthalene-3,6-disulfonic acid,

l-amino-8-hydroxynaphthalene-4,6-disulfonic acid and l-(N-ethylamino)-8-hydroxynaphthalene-3,6-disulfonic acid.

Suitable isocyanates and carbamic acid derivatives of Formula 6 or 7 respectively which may be used for the reaction with the naphthalene derivatives of Formula 5 are for example 4-vinylsulfonylpheuyll-isocyanate, 3 -vinylsulfonylphenyll-isocyanate, 4-( 8-chloroethylsulfonyl)-phenyl-1-isocyanate, 3- p-chloroethylsulfonyl -phenyl-l -isocyanate, 2- (fl-chloroethylsulfonyl)-pheny1-l-isocyanate,

moreover ,3 hydroxyethylsulfonyl phenylisocyanates wherein the hydroxy group in it-position is esterified for example with methane-sulfonic acid, benZene-sulfonic acid, para-toluene-sulfonic acid or acetic acid, 3- or 4- (fi-phenoxy-ethylsulfonyl)-phenyl-l-isocyanate as well as the condensation products of 1 mol of chloroformic acid phenylester with 1 mol of 3- or 4-aminophenyl-1-(18- sulfatoethyl)-sulfone.

If the amines, the diazo compounds of which are used for the preparation of the metal-free dyestuffs of Formula 1 contain in ortho-position to the amino group a grouping capable of forming metal complexes or of being converted into such a grouping, for example a carboxyl group, a hydroxy group or an alkoxy group such as a methoxy group, the metal-free dyestuffs obtained which correspond to Formula 1 can be transformed by known methods into their metal complexes, for example their copper, nickel, chromium or cobalt complexes. For the preparation of the metal complex compounds the o,o'-dihydroxy-azodyestutfs or o-carboxy-o-hydroxy-azo dyestuffs obtainable according to the process of the present invention are reacted with an agent yielding metal. If desired, the metal complex compounds of o,o-dihydroxy-azo dyestuffs can also be obtained in an indirect manner by coppering o-alkoxy-o'-hydroxy-azo dyestuffs with den alkylation or by treating o'-hydroxy-azo dyestuffs which contain a hydrogen atom in ortho-position to the azo bridge in a weakly acid solution with copper salts and with an oxidizing agent. Subsequently, the copper complex compounds obtained in this manner can be decoppered, if desired, for example by treatment with mineral acids, and then converted into the metallized o,o'- dihydroxy-azo dyestuffs by means of another agent yielding metal.

As agents yielding metal there may be used according to the process of the invention compounds which yield copper, nickel, chromium or cobalt. Suitable for this purpose are, for example, the salts of the metals cited, for instance chromium sulfates, cobalt acetate, cobalt sulfate, copper acetate or copper sulfate. There may, however, also be used metallizing agents containing complexbound metal, such as for example complex chromium or cobalt compounds of aliphatic hydroxycarboxylic acids or dicarboxylic acids and chromium complex compounds of aromatic o-hydroxycarboxylic acids such, for example, as salicylic acid, moreover complex cobalt or copper compounds of the alkali metal salts of aliphatic hydroxycarboxylic acids. Suitable aliphatic hydroxycarboxylic acids are, for example, citric acid, lactic acid, glycolic acid, and above all, tartaric acid.

The reaction of the metal-free azo dyestuffs of the general Formula 1 with the agents yielding metal is advantageously carried out in the heat. It is expedient to heat the aqueous metallization mixture in a weakly acid to neutral range to temperatures between 20 C. and 130 C., if desired under reflux or in a closed vessel. If necessary, organic solvents such as alcohol or dioxane may be added or the reaction may be carried out in the presence of further agents accelerating the formation of complexes such, for example, as the salts of organic acids.

The metal complex dyestuffs obtainable according to the :process of the present invention may contain one complex-bound metal atom each in 1 or 2 dyestufi molecules. In the case of chromium or cobalt the molar ratio of the metal to the azo dyestuff is preferably 1:2, whereas the complex compounds obtained with the use of agents yielding copper or nickel contain one metal atom per molecule of dyestufi.

The formation of the dyestuffs of the general Formula 1 can likewise be achieved by reacting metal-free azo dyestuffs of the general formula wherein D, R and n are defined as above and which contain an amino group capable of being acylated, with isocyanates of Formula 6. If desired, the metal-free dyestuffs obtained-provided they contain in ortho-position to the azo bridge a hydrogen atom or a substituent capable of forming metal complexes or of being converted into a substituent of this kindmay then be converted by a further reaction step into their metal complex compounds. The necessary starting substances of Formula 8 can be obtained in simple manner by coupling the diazonium compound of any aromatic amine with a coupling component of Formula 5.

According to a particular variation of the process described for the manufacture of metal complex dyestuffs of Formula 1 it is advantageous to metallize the starting substances of Formula 8-provided they meet the abovementioned requirements for the formation of metal complexes-according to known methods, prior to the reaction with the isocyanates of Formula 6.

The reaction described above is preferably carried out by adding an isocyanate of Formula 6 at a relatively low temperature, advantageously within the range from about 5 to +30 C., and with stirring, to the aqueous solution of the metal-free starting dyestutf of Formula 8, which contains an amino group capable of being acylated, or the metal complex compound thereof, the solution showing a weakly alkaline or weakly acid, preferably a neutral reaction. The acylating components of Formula 6 can be used as such, for example in the form of a powder, if desired with addition of an emulsifier in order to obtain a better degree of dispersion in the aqueous phase, or dissolved in a suitable organic solvent such as benzene, toluene, chlorobenzene or acetone.

A further variation of the process of the invention consists in subjecting the grouping Z of the metal-free azo dyestuffs of Formula 1 obtained according to the process of the invention as well as of their metal complex compounds or, above all, of the coupling components of Formula 4 used for the preparation of said dyestuffs, prior to the coupling to further reactions within the limits indicated by the groups of Formulae 2 and 3. Thus it is possible, for instance, to convert the vinylsulfonyl group of Formula 2 by reaction with a salt of thiosulfuric acid in a weakly acid aqueous medium into a ,B-thiosulfatoethylsulfonyl group corresponding to the above Formula 3, or to modify the substituent X of Formula 3, for example by exchanging a halogen atom against a dialkylamino group.

The products of the invention may be isolated from the medium in which they were formed either in their metalfree form or as complex compounds, according to known methods, for example in the form of an alkali metal salt by salting out with sodium or potassium chloride, or by spray-drying of the neutralized reaction mixture.

In the form of their alkali metal salts the dyestuffs obtained according to the process of the invention are soluble in water and may be used for dyeing and printing various kinds of materials, for example silk, wool, leather, synthetic polyamides and polyurethanes, regenerated protein and cellulose materials, in the first place, however, cotton, linen and viscose rayon. The metal-free monoazo dyestuffs obtainable according to the process of the invention are of particular value in that they are excellently suitable for the preparation of fast red dyeings, in particular on textiles made of cellulose. The new dyestuffs are applied to the material to be dyed in the presence of acid-binding agents according to the dyeing and printing processes generally used in industry. They may also be used for the dyeing of wool, silk, regenerated proteins, polyamides and modified acrylonitrile materials accovding to the usual dyeing processes in weakly acid, neutral or weakly alkaline dyestutf solutions. The dyeings and prints obtained with the use of these dyestuffs are usually distinguished by high tinctorial strength, purity of shade, a good fastness to light and especially by a very good resistance to washing.

If the dyestuffs contain groups capable of forming metal complexes, for example o-hydroxy-o-carboxy groups, o,o'-dihydroxy groups or o-hydroxy-carboxy groups which are present for example in salicylic acid derivatives, the metal-free dyeings may be treated on the material with agents yielding metal.

The following examples illustrate the invention but they are not intended to limit it thereto, the parts and percentages being by weight unless otherwise mentioned and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

Example 1 223 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 700 parts by volume of water while adding sodium carbonate to give a neutral solution. Into the solution thus obtained which has been cooled to 0 to +5 C. a solution of 206.5 parts of 3-(fi-chloroethylsulfonyl)-phenyl-l-isocyanate (melting point 81 C.) in 415 parts of acetone is introduced within one hour while A part of the saline filter residue which corresponds to 56.5 parts of the coupling component of the above for mula in the form of its free acid, is dissolved in 1,000 parts by volume of water and combined, at to C., with an ice-cold solution of a diazonium salt obtained 100 parts by volume of water and filtered at C. The filtrate which contains the coupling component of the following formula SOglI in the form of the disodium salt, is cooled to 010 C. and combined with an aqueous solution of the diazonium compound of 8.65 parts of 1-arninobenzene-4-sulfonic acid. The pH-value of the coupling mixture is then adjusted to 6-7 by means of sodium bicarbonate and when the coupling is complete sodium chloride is added. The precipitated trisodium salt of the dyestulf which in the form of the free acid corresponds to the following formula from 9.3 parts of l-aminobenzene, 24 parts of 37% hydrochloric acid, 100 parts of ice and 7.0 parts of sodium nitrite. The pH-value of the coupling mixture is adjusted to 6-7 by addition of sodium carbonate. When the coupling is complete sodium chloride is added to the mixture; the dyestuff which has been salted out is filtered, washed with dilute sodium chloride solution and dried in vacuo at 50 C. In the form of its free acid the dyestuff corresponds to the following formula The dyestuff obtained is a dark red, water-soluble powder which according to the direct dyeing or the pad-dyeing method dyes cotton strong red shades fast to washing and to light.

The new dyestuff is also suitable for dyeing polyamide fibers and wool in an acid bath, bright red shares of good fastness to light and to washing.

Example 2 15.95 parts of l-amino-8-hydroxynaphthalene-4,6- disulfonic acid are dissolved in 100 parts by volume of water, while adding sodium hydroxide solution, to give a neutral solution. 12.5 parts of finely pulverized 4-vinylsulfonyl-phenyl-l-isocyanate (melting point 61 C.) are strewed into the solution at 0 to 10 and at a pH-value of 6.5 to 6.8, while vigorously stirring. As soon as no more starting material is detectable the mixture is diluted with is filtered, washed with dilute sodium chloride solution and dried. It is a red powder which produces brilliant red prints on cotton having a good fastness to Wet processing and to light.

When the coupling component prepared as described above is treated with sodium thiosulfate in aweakly acid aqueous solution or reacted in an alkaline medium with diethylamine prior to coupling it with l-aminobenzenelsulfonic acid and the process is continued as described above, there are obtained the dyestuffs of the following formula SOsH wherein Z represents a thiosulfuric acid ester group or a diethylamine group, which have similar good properties. The following table contains a number of further azo dyestuffs obtainable according to the process of the invention which can be prepared in the manner described in Examples 1 and 2 by coupling one of the coupling components given in column I with one of the diazo components of column II. The dyestuffs dye cotton by the direct dyeing process or the pad-dyeing process as well as by the printing process the shades specified in column III which are fast to wetting. In the structural formulae of the coupling component R represents the grouping and R represents the grouping I II III N0. Coupling component Diazo component Tint on cotton 16 HO R Red.

| I O:N NH2 I S 03H 17 Same as No. 16 above Do.

18 .d0 Bluish red.

19 ..d0 50311 Red.

NHg

20 .do 810311 Bluish red.

91 dn I'IOBIS Greenish blue.

E0 S S 0 11 22 dn SiO H Violet.

92 do S|O31I Blue.

H O;;SN=N NH1 l S 0 H 24 d0 N\ Red.

t S S 0 H 25 .do no /N\ $0311 Do.

| S S 0 H 26 d0 Hoa? Blue.

27 ..do Do.

-NH NH:

28 d0 H01? Do.

HaC-C ONHNH--NH2 I II III No. Coupling component Diazo component Tint on cotton 29 .do (IJCH; Bluish red.

3O d tTiOsH Red.

mo OQ-NH:

31 do S|O H Do.

l CH3 32 ..do D0.

HOaS-Q-NH:

33 --do ?O3EI Do.

34 .d0 Do.

NH-C O-NH2 SOaE I 35- .do 01 D o.

l S 03H 0:

N C-NH- NH1 (ll-N C1 l S OzNH2 37- ..do IOa Violet.

Example 3 16.0 parts of 1-arnino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 300 parts by volume of water at a pH value of 6.5-6.8 while adding sodium hydroxide solution. 19 parts of 2-(fi-chloroethylsulfonyl)-phenyl-1- isocyanate (viscous oil) are then added while stirring and stirring is continued for 6 hours at 0-10" C. After addition of 700 parts by volume of water the solution is filtered and the reaction product isolated by salting out with sodium chloride and subsequent filtration.

The moist filter cake obtained is added to a cold diazonium salt solution which is prepared by diazotization of the solution of 4.66 parts of l-arninobenzene in parts of water and 12 parts of 37% hydrochloric acid with an aqueous solution of 3.45 parts of sodium nitrite. When the coupling is complete the solution is diluted with 1,000 parts by volume of Water and the pH value is then adjusted to 6-7 by addition of concentrated sodium carbonate solution. The dyestuif which in the form of the free acid corresponds to the following formula Example 4 16.0 parts of l-amino- -hydroxynaphthalene-3,6-disul- 1 fonic acid are dissolved in 200 parts by volume of Water while adding sodium hydroxide solution to give a neutral solution. parts of 4-(,8chloroethylsulfonyl)-phenyl-1- isocyanate (melting point 100 C.) are introduced in the form of a powder at 0 to 10 C. and the whole is first stirred for 10 hours at 0-10 C. and a pH value of 67 and then for another 24 hours at room temperature. Subsequently, 5 parts of kieselguhr are added to the mixture,

biO lI HOiS- S0311 the whole is heated to C. while stirring, and filtered. The product is salted out by addition of sodium chloride, filtered and washed with a dilute sodium chloride solution.

The moist filter residue obtained is added to a diazonium salt solution which is prepared in the following manner: 6.9 parts of aniline-Z-carboxylic acid are diazotized at 0-5" C. in parts by volume of water and 12 parts of 37% hydrochloric acid with 3.5 parts of sodium nitrite, and the pH value is then adjusted to 5-6 by means of sodium bicarbonate.

The coupling is allowed to terminate at a pH value of 6 to 7 and the precipitation of the dyestuff formed is then completed by addition of sodium chloride. The product is isolated in the usual manner and dried under reduced pressure at 40 C.

The new dyestulf which corresponds to the following formula dyes cotton in the presence of sodium hydroxide clear, bluish red shades which show a good fastness to washing.

Example 5 160 parts of 1 amino 8 hydroxynaphthalene-3, 6- disulfonic acid are dissolved in 200 parts by volume of water while adding sodium hydroxide solution to give a neutral solution. 30 parts of pulverized N [4-(fi-sulfatoethylsulfonyl-phenyl] l-carbamic acid phenylester (obtained by condensation of chloroformic acid phenylester with 4 aminophenyl I-;9-hydroxyethylsulfonesulfuric acid ester) are then added to the solution at 50-60 C. and at a pH-value between 6.7 and 7.3, while vigorously stirring. When the 1 amino 8 hydroxynaphthalene- 3,6-disulfonic acid is no more detectable in the reaction mixture by paper chromatography, the solution is diluted with 100 parts by volume of water, filtered and the product salted out with sodium chloride. The precipitate is then filtered, Washed with a dilute sodium chloride solution and redissolved in 300 parts by volume of Water.

The solution of the coupling component obtained in this manner is then combined at 0-10" C. with a neutralized diazonium salt solution which is prepared by diazotization of 11.1 parts of Z-arninonaphthalene-l-sulfonic acid in parts by volume of water and 18 parts of 37% hydrochloric acid, at 05 C., with 3.5 parts of sodium nitrate. The mixture is then stirred at a pH-value of 6-7 until the coupling is complete, the dyestufi is separated by addition of sodium chloride, filtered and dried. In the form of its free acid the dyestuff obtained corresponds to the following formula As tetrasodium salt it dissolves readily in Water and dyes cotton brilliant bluish shades which are very fast to washing and to light.

The dyestufi of the above formula can also be prepared by reacting the condensation product of 1 mol of l-amino- 8-hydroxynaphthalene-3,6-disulfonic acid and 1 mol of chlorofor-mic acid phenylester in an aqueous solution at a pH-value of 7.0-7.3 and at a temperature of 55-60 C. with 1 mol of 4-aminophenyl-1-(fi-hydroxyethyl)-sulfonesulfuric acid ester. There is obtained the coupling component of the following formula NH-C O-NH HOsS SOaH which, after salting out with potassium chloride, is coupled with the corresponding amount of diazotized 2- naphthylamine-l-sulfonic acid.

Example 6 (a) 16.0 parts of 1 amino 8 hydroxynaphthalene- '3,6-disulfonic acid are dissolved in 200 parts by volume of water while adding sodium carbonate to give a neutral solution. 13 parts of 3-vinylsulfonyl-phenyl-l-isocyanate (melting point 46 C.) are then introduced in the form of a powder at a pH-value of 6.5-7.0 and at 0-10 C., while stirring vigorously. When the reaction is terminated the condensation mixture is diluted with 100 parts by volume of water and filtered, and sodium chloride is added to the filtrate. The precipitate formed is then filtered and redissolved in 200 parts by volume of water.

(b) 13.2 parts of 4 aminodiphenylarnine-3-sulfonic acid are dissolved in 100 parts by volume of water while adding sodium hydroxide solution to give a neutral solution; the solution is then poured onto a mixture of 18 parts of 37% hydrochloric acid and 100 parts of ice and diazotized at 0-5 C. with 3.5 parts of sodium nitrite.

The solution of the coupling component obtained as described in paragraph (a) is then introduced at 010 C. into the diazonium salt suspension obtained and the pH-value of the coupling mixture is adjusted to 6-7 by strewing in sodium bicarbonate. The dyestulf formed which in the form of the free acid corresponds to the following formula SOsH H? 3,419,542 17 18 is salted out in the form of the tri-potassium salt by addi- Example 9 tion of potassium chloride, filtered and dried. The dyestutf obtained dyes cotton blue shades of good fastness to wet processing.

31.9 parts of 1-amino-S-hydroxynaphthalene-S,6-disulfonic acid are dissolved in 400 parts by volume of water while adding sodium hydroxide solution to give a neutral Example 7 solution. 26 parts of 4-vinylsulfonylpheuyl-l-isocyanate 12.8 parts of 1 -amino 8 hydroxynaphthalene-3,6- are then strewed in in the form of a powder at 0 to 20 C. disulfonic acid are dissolved in 50 parts by volume of and at a pH-value of 6.5-6.8. The reaction mixture is water while adding sodium hydroxide solution to give a stirred until no more free amino groups are detectable,

neutral solution. 15 parts of 3 (/8 phenoxyethylsulit is then diluted with 400 parts by volume of water and fonyl)-phenyl-l-isocyanate (melting point 87 C.) are 10 filtered, and the addition product salted out with sodium then strewed in the form of a powder at 0-10 C. and chloride. The precipitate is filtered and washed with dilute the reaction mixture is first stirred for 10 hours at 0- sodium chloride solution. 10 C. and then for another 24 hours at room tempera- The moist filter residue obtained is now dissolved in ture and at a pH-value between 6 and 7. The mixture 1,000 parts by volume of water and added to the solution is then diluted with 200 parts by volume of water and or suspension of the diazonium salt of 15.4 parts of 4- filtered, and potassium chloride is added to the filtrate. nitro-2-amino-l-hydroxybenzene which has been adjusted The precipitate formed is filtered and washed with dilute to a pH-value of 6-7. The coupling is allowed to termipotassium chloride solution. nate at a pH-value of 6.5-7.0, the pH-value of the mix- The moist filter residue obtained in this manner is then ture is then adjusted to 4-5 by means of hydrochloric introduced into a diazonium salt solution prepared by acid, sodium chloride is added and the precipitated dyediazotization of 6.9 parts of 1-aminobenzene-4-sulfonic stuff is filtered with suction. acid. The coupling is allowed to take place at 0-10 C. The moist filter cake of the metal-free monoazo dyeand at a pH-value of 6-7. Finally, the dyestufi formed is stufl' obtained is dissolved in 1,000 parts by volume of salted out in the form of the trisodium salt by addition of water, 25.0 parts of chromium alum are added and the sodium chloride, filtered and dried. In the form of the free pH-value of the solution is adjusted to 5-6 by addition acid it corresponds to the following formula of sodium acetate. The solution is thenstirred at 80 C.

and dyes cotton red shades which are fast to washing. until the formation of the chromium complex is terminated. Subsequently, the product is salted out with sodium ple 8 chloride at room temperature, the chromium complex dyestutf precipitated is filtered and dried in vacuo at 50 C. 11.2 parts of 6-chlpro-2-arn1no-1-hydroxybenzene-4- The 2:1-ch10miurn complex dyestuif obtained which sulfonic acid are drazotized in a mixture of 12 parts of it et all free d f d t th f 11 37% hydrochloric acid and 100 parts of ice with 3.5 l i an am orm correspon s 0 e o parts of sodium nitrite. The pH-value of the diazonium mg 0mm a salt solution is then adjusted to 6-7 by means of sodium carbonate, and the solution of 28 parts of the coupling H0 H0 S 2C r component described in Example 1 in 500 parts by volume of water is added. The coupling mixture is stirred for about 24 hours at 0 to 20 C. and at a pH-value of 6.5-7.0 until the coupling is complete, the pH-value Hoasis then adjusted to 4-5 by addition of hydrochloric acid, sodium chloride is added and the precipitated metal-free N01 dyestuif is then filtered with suction.

The moist filter cake obtained is stirred into 500 parts 3 2 sg. prints on cotton Whlch are fast m by volume of water, an aqueous solution of 12.5 parts of g a Wa crystallized copper sulfate is added, and the pH-value of Example 10 the metallization mixture is adjusted to 4.5-5.5 by addition of sodium acetate. The solution is then stirred for 1 parts f h h l -5. 1- about 2 hours at q ifi the P is fonic acid are mixed by stirring with 500 parts by volume p to 6 h) meahs 0f sodlhm Carbonate, the Product of water and the whole is neutralized by addition of about Is salted out w1th sod1um chloride and filtered. The dye- 6 parts f sodium hydroxide solution Aft cooling stuff is washed with dilute sodium chloride solution and C 5 parts f 3-(fi hl ro thyl ulfonyl).phenyldried at under Te'dueed pressure In the form of l-isocyanate in the form of a powder are strewed in and the free 9 the metal eompleX dyesmfi corresponds to the batch is stirred for 12 hours, while cooling, at a pH- followmg formula value of 6.5-7.0. If the reaction product contains still on unreacted starting product another 15 parts of the isocyanate are introduced and the batch is once more stir-red I for 12 hours at room temperature and at a pH-value of 1.-

C 6.5-7.0. Subsequently, the whole is diluted with 1,300

parts by volume of water, the solution is filtered and sodium chloride is added to the filtrate. The preci itate of H033 S0311 Sol-CH2 01 the addition product is filtered with suction and washed 80311 with an aqueous sodium chloride solution.

The moist filter cake of the coupling component ob- It yields violet dyeings and prints on cotton, having a good tained in this manner is introduced into 200 parts by fastness to light and to washing. volume of water, the solution is cooled to 0-5 C. and a diazonium solution is added which is prepared in the following manner: 19 parts of l-aminonaphthalene-3,5,7- trisulfonic acid are diazotized at -5 C. in 200 parts by volume of water and parts of 37% hydrochloric acid with an aqueous solution of 3.5 parts of sodium nitrite. The excess nitrous acid is then decomposed by addition of amidosulfonic acid and the excess acid is neutralized by means of sodium carbonate.

Subsequently, the coupling is allowed to terminate at 0-5 C. and at a pH-value of 6-7. A solution which contains parts of potassium acetate in 80 parts of methanol is added to the coupling mixture until the dyestul'f formed, which in the form of the free acid corresponds to the following formula dyestulr" is obtained which in the form of the free acid corresponds to the following formula It dyes cotton brown shades which are more reddish than those obtained with the dyestuff prepared according to Example 11.

has largely precipitated. The precipitate is filtered with suction, washed with methanol and dried in vacuo at 50 C.

The dyestuff which is obtained in the form of a powder yields reddish violet prints on cotton, having a good fastness to wet processing.

Example 11 11.96 parts of l-amino-8-hydroxynaphthalene-3-sulfonic acid are dissolved in 200 parts by volume of water at a pH-value of 6-7 while adding a 33% sodium hydroxide solution. A solution of 20 parts of 3-(fl-chioroethylsulfonyl)-phenyl-1-isocyanate in parts of chlorobenzene is added at room temperature and the whole is stirred for 24 hours at a pH-value between 6 and 7. The reaction mixture is diluted with 300 parts by volume of water, 10 parts of kieselguhr are added, and the solution is clarified by filteration at C. The addition product formed is salted out with sodium chloride, the precipitate filtered with suction and washed with a dilute aqueous sodium chloride solution.

The filter residue of the coupling component obtained in this manner is dissolved in 500 parts by volume of water and the solution is reacted at 0-5" C. and at a pH-value of 6-7 with the suspension of a diazonium salt which is prepared by the diazotization of 15.1 parts of 2-aminonaphthalene-4,8-disulfonic acid.

When the coupling is complete the dyestufi formed, which in the form of the free acid corresponds to the folis salted out with sodium chloride, filtered with suction and dried. It produces bluish brown prints on cotton.

Example .12

When using, in Example 11, instead of 1-amino-8- hydroxynaphthalene-3-sulfonic acid the same amount of 1-amino-8-hydroxynaphthalene-4-sulfonic acid and instead of 15.1 parts of 2-aminonaphthalene-4,8-disulfonic acid 12.7 parts of 1-amino enzenef n acid, a

Example '13 25.3 parts of 1-aminobenzene-2,5-disulfonic acid are dissolved in 200 parts by volume of hot water, the solution being neutralized by addition of 33% sodium hydroxide solution. 25 parts of 37% hydrochloric acid are added and the amino component is then diazotized at 0-S C. by means of an aqueous solution of 6.9 parts of sodium nitrite. The pH-value of the diazonium mixture is adjusted to 2-3 by strewing in sodium bicarbonate and then combined while stirring at 0-5 C. with the filtered solution of 13.7 parts of 3-amino-4-methoxy-1-methylbenzene in 50 parts by volume of 2 N hydrochloric acid, the pH-value being maintained between 2 and 3 by continuous addition of sodium bicarbonate. The mixture is still stirred for some hours at 0-5 C. until the coupling is complete.

The pH-value of the coupling mixture obtained in this manner which contains the monoazo dyestutf of the following formula SIOzH (RCH:

is then adjusted to 6.0-6.5 by means of sodium carbonate and the mixture diluted with 750 parts by volume of water. The almost clear solution obtained is filtered, 25 parts of 37% hydrochloric acid are added, causing the formation of a thick precipitate, and the aminoazo dyestuff is diazotized at 0-5 C. with an aqueous solution of 6.9 parts of sodium nitrite. The pH-value of the diazo mixture is then adjusted to 5-6 by means of sodium bicarbonate. For the preparation of the disazo dyestuif the mixture is reacted with a cold neutral solution of 56.5 parts of the coupling component of the following formula prepared as described in Example 1, in 700 parts by volume of water. The coupling is terminated at a pH- value of 6-7, the precipitation of the disazo dyestufi formed is completed by addition of sodium chloride, and the precipitate filtered with suction and dried.

The dyestufi? obtained which in the form of the free Example 16 acid corresponds to the following formula 34.7 parts of 1-(N-ethylamino)-8-hydroxynaphthylenel SOaH CH: HOaS- SO2-CH2-CH2C1 produces navy blue dyeings and prints on cotton. 3,6-disu1fonic acid are dissolved in 500 parts by volume of Water while adding a 33% sodium hydroxide solution Example 14 to give a neutral solutlon. A solutlon of 40 parts of 3- Parts of the red dyfistuif 0f the formula (fichloroethylsulfonyl)-phenyl-1-isocyanate in 80 parts of chlorobenzene is added, and the reaction mixture is OH stirred for about 12 hours at room temperature and at a pH-value between 6.5 and 7.0. After addition of parts I l of kieselguhr the solution is clarified by filtration and the product salted out with potassium chloride. The precip- Hoas itated coupling component is separated from the liquid components of the mixture by filtration or decanting, S0311 washed with an aqueous potassium chloride solution and dissolved in 400 parts -by volume of water. The solution obtained is cooled to '0-5 C. and combined with an ice cold diazonium solution of 9.3 parts of aniline. The pH- value of the mixture is adjusted to 6.5-7.0 by means of sodium bicarbonate, and when the coupling is complete the product is salted out with potassium chloride. The dyestulf is filtered with suction and dried. In the form of the free acid it corresponds to the following formula which is specified in the table following Example 2, are dissolved in 1,500 parts by volume of water to give a neutral solution. 22.5 parts of copper sulfate containing crystal water and 22.5 parts of anhydrous sodium acetate are added, and 11.3 parts of hydrogen peroxide solution are dropped into the metallization mixture within 3 one hour at a pH value of 5.0-5.2 and at a temperature of 2025 C. In order to complete the oxidative coppering the batch is stirred for another 12 hours approximately, the metallized dyestulf is salted out with sodium chloride, filtered with suction, washed with a dilute aqueous 35 sodium chloride solution and dried at 50 C. under C2H5 reduced pressure. The copper complex dyestulf obtained OH l produces reddish violet prints and dyeings on cotton I having a good fastness to light and to wetting.

H038 SOaH SO:CHzCHa-Cl Example 15 50 parts of the monoazo dyestutf of the following formula OH N11 l I NaO3S@N=N It dyes and prints cotton clear red shades of good Wet I fastness properties. NaOaS SOQNa which is obtained by coupling equivalent amounts of Example 17 diazotized 1-aminobenZene-4-sulfonic acid and of 1- amino-8-hydroxy-naphthalene-3,6-disulfonic acid in an 18.9 parts of Z-amino-1-hydroxybenzene-4-sulfonic alkaline medium, aredissolved in 400 parts by volume of acid are dissolved in 250 parts by volume of water, while water, the solution of 50 parts of 3-(fl-chloroethylsuladding sodium hydroxide solution to give a neutral solufonyl)-phenyl-l-isocyanate in 100 parts of chlorobenzene tion. 25 parts of 37% hydrochloric acid and 100 parts of is added at 20 C. and the reaction mixture is stirred for ice are added, and the whole is diazotized at 0-5" C. about 12 hours at a pH-value of 6.5-7.0. with an aqueous solution of 6.9 parts of sodium nitrite.

After dilution with 500 parts by volume of water and The pH-value of the diazonium mixture is adjusted to addition of 2 0 parts of kieselguhr the solution is clarified 45 by means of sodium carbonate, and the diazo soluby filtration and the dyestuff formed salted out by addition is introduced, while thoroughly stirring, into a cold tion of sodium chloride. In the form of the free acid the solution of 31.9 parts of l-amino-S-hydroxynaphthalenedyestuff corresponds to the following formula 3,6-disulfonic acid in 100 parts by volume of water, to

The precipitate is filtered with suction, washed with a which have been added 15 parts of sodium carbonate dilute aqueous sodium chloride solution and dried at 50 after neutralization. The coupling takes place very rapidly. C. In the presence of alkaline agents the dyestulf de- After stirring for another 5 hours the pH-value of the scribed yields clear, bluish red dyeings and prints on cotcoupling mixture is adjusted to 6-7 by means of hydroton which are fast to washing. chloric acid. Subsequently, sodium chloride is added 23 24 and the precipitated dyestuif which in the form of the pling component is obtained which in the form of the free free acid corresponds to the formula acid corresponds to the following formula OH OH NH:

I OH NHoo-NH-so,-orr=oH A HOsS 803E I H038 'SO3H S0311 is filtered with sucti n. 52.9 parts of the coupling component of the above For the metallization the moist filter cake obtained in fOrmllla a d S IVe in t e fo m of the disodium salt in this manner is dissolved in 500 parts by volume of water, 350 Parts Of Water to give a neutral Solution and heated 14 parts of cobalt sulfate containing crystal water are to At this temperature Parts of Sodium added, and the pH-value of the solution is adjusted t thiosulfate containing crystal water are added while stir- 5.5-6.0 by addition of sodium carbonate. The metallizaring, the pH-value being maintained within the ran e tion mixture is then stirred at room temperature for about om -8 t 6.3 by dropping in 50% acetic acid. Stir- 12 hours in the course of which the 1:2-cobalt complex ring is continued for 3 hours at the above pH-value and of the above monoazo dyestuff is formed. The end of the emperature, then the product is salted out at room temreaction can be easily recognized by chromatography on perature by means of sodium chloride, filtered with sucpaper. tion and washed with a dilute aqueous sodium chloride The pH-value of the solution of the cobalt complex dyesolution. stuff is adjusted to 6.5-6.8 by addition of sodium car- T m i t fil r r sidue is dissolved in 350 parts of bonate and a solution of parts of 3-(B-chloroethylwater and coupled at a pH-value of 6-7 with the diazosulfonyl)-phenyl l-isocyanate in 60 parts of chlorobennium salt solution of 9.3 parts of aniline. A dyestuff is zone is added. After stirring for 12 hours at room temobtained which in the form of the free acid corresponds perature and at a pH-value of 6.5-6.8 and after addition 30 to the following formula l HOaSk/ 80111 of 10 parts of kieselguhr the solution is clarified by filtra- The dyestutf is salted out with sodium chloride, filtered tion and the filtrate is concentrated to dryness by evaporawith suction and dried in vacuo at C. tion in vacuo at 50 C. The metal complex dyestuif is thus In the presence of acid-binding agents the dyestufi isolated in the form of a powder. In the metal-free and dyes cotton red shades of good wet fastness properties. acid form the 1:2-cobalt complex dyestuff corresponds to When dissolving 52.9 parts of the above coupling comthe following formula ponent in the form of the disodium salt in 350 parts of Water to give a neutral solution, adding 14 parts of di- OH OH NHC O H ethylamine, keeping the temperature of the batch Within A l the range from 20 to 30 C. and the pH-value for 4 N= hours between 10.5 and 11.0 by addition of sodium hydroxide solution, salting out the product with sodium aS S a S I chloride, washing the filtered precipitate with sodium chloride solution and coupling the solution of the moist I SOa filter residue in 350 parts of water at a pH-value of 6.5-

It produces violet prints on cotton. 7.0 with the diazonium salt of 17.3 parts of l-a-minobenwhen using 25 parts of chromium alum instead of c zene-4-sulfonic acid, a dyestuif iS obtained which in the balt sulfate, heating during the metallization to 8590 (3. form of the free and corresponds to the followmg formula on r m-o O-NH-QSOPCHPCHPNKHHO 2 Hois A fiossk/ 80311 and proceeding as described above there is obtained the In the presence of an alkali, for example sodium carl:2-chron:ium complex of the dyestuflf of the formula bonate or sodlum hydroxide, the dyestufi yields red prints given above. This dyestult' can be salted out with potason cotton which are fast to wet processing.

sium chloride and yields navy blue prints on cotton.

Example 19 Example 18 (a) 319 parts of 1-amino-8-hydroxynaphthalene-3,6-

When using in Example 2 instead of 1-amino-8-hydisulfonic acid are dissolved in 1,500 parts of water while droxynaphthalene-4,6-disulfonic acid the same amount of adding 33% sodium hydroxide solution to give a neutral l-amino-8-hydroxynaphthalene-3,6-disulfonic acid a cousolution. At 40 C. a warm solution of 296 parts of 3-(pchloroethylsulfonyl)phenyl-I-isocyanate in 650 parts of chlorobenzene is introduced while stirring and the batch is stirred at a pH-value of 6-7 until the l-amino-S-hydroxynaphthalene-3,6-disulfonic acid has completely reacted. The chlorobenzene is then removed from the reaction mixture by distillation in vacuo.

(b) 303 parts of Z-aminonaphthalene-1,5-disuifonic acid are mixed by stirring with 1,000 parts of water, 2,000 parts of ice and 150 parts of 37% hydrochloric acid are added, and the whole is diazotized at -5 C. by treat- 10 ment with 173 parts of 40% sodium nitrite solution. After about 30 minutes a slight excess of nitrite is decomposed by means of amidosulfonic acid. Then the solution of the coupling component obtained according to (a) which is free from chlorobenzene and has a temperature of about C. is added, and the pH-value of the coupling mixture is adjusted to 6.5-7.0 by addition of saturated aqueous sodium carbonate solution and maintained at this value. When the coupling is complete the mixture is diluted to 12,000 parts by volume by addition of water, 20 filtered, and sodium chloride is added to the filtrate. The precipitated dyestuif which in the form of the free acid corresponds to the following formula HOaS- SOaH SO2CH2-CHr-Cl H MS Example 20 When using, in Example 19 instead of 296 parts of 3- (fi-chloroethylsulfonyl)-phenyl-1-isocyanate 335 parts of 45 3 (B-acetatoethyl-sulfonyl)-phenyl-1-isocyanate (viscous substance) and proceeding further as described in said example a dyestuif is obtained which in the form of the free acid corresponds to the following formula Example 22 44 parts of the dyestuff of the formula given in Example 21 are mixed by stirring with 1,000 parts of water, and 22.5 parts of copper sulfate containing crystal water are added. The pH-value of the mixture is adjusted to 5.0-5.2 by addition of sodium acetate, and Within 2 hours, at 20-25 C., 11.3 parts of a hydrogen peroxide solution are dropped in, the pH-value being maintained by further addition of sodium acetate. The batch is stirred overnight, the complex compound salted out with sodium chloride and the precipitated dyestutf, which in the form of the free acid corresponds to the following formula Cu 11038 c I IYIH-CO-NH C] N=N- q l Ho3s- HOaS- SOaH SOs-CHz-CHz-Cl is filtered. The filter residue is washed with a dilute aqueous sodium chloride solution and dried in vacuo at 60 C.

There is obtained a dark blue dyestuif powder which yields blue dyeings and prints on cotton, having good properties of wet fastness and an excellent fastness to light.

Example 23 (a) 319 parts of 1-amino-8-hydroxynaphthalene-3,6- disulfonic acid are dissolved in 1,500 parts of water while adding 33% sodium hydroxide solution to give a neutral solution. A solution of 335 parts of 3-(,8-acetatoethyl-sulfonyl)-phenyl1-isocyanate in 650 parts of chlorobenzene is added with stirring and stirring is continued at a pH-value of 6-7 until the l-amino-S-hydroxynaphthalene-3,6-disulfonic acid has reacted. The chlorobenzene is then removed from the reaction mixture by distillation in vacuo.

(b) 93 parts of aniline are added to a mixture consisting of 200 parts of water, 500 parts of ice and 250 parts of 37% hydrochloric acid and the whole is diazotized at 0-5 C. by treatment with 173 parts of 40% sodium nitrite solution. After about 30 minutes a slight excess of nitrite is destroyed by addition of amidosulfonic acid. The solution of the coupling component, obtained acand which is equal to the dyestuff of Example 19 as regards properties and shade.

Example 21 When using in Example 19 instead of 303 parts of 2- aminonaphthalene-1,5-disulfonic acid 303 parts of 2- aminonaphthalene-6,8-disulfonic acid and continuing the operation as described a dyestuif is obtained which in the form of the free acid corresponds to the following formula lT1HCO-NH-@ l 1 SOsH H 33- HOZS- S OrCHa-OHz-Cl oiifu Example 24 When using in Example instead of 11.1 parts of 2- aminonaphthalene-l-sulfonic acid 15.1 parts of Z-aminonaphthalene-1,5-disulfonic acid and proceeding further as described in said example, there is obtained a dyestutf which in the form of the free acid corresponds to the following formula HO 1 @S t HOsS S0311 1103 s The product dissolves excellently in water and yields clear bluish red dyeings and prints on cotton, having good properties of wet fastness and, in particular, a good fastness to bathing water containing chlorine.

Example 25 (a) 159.5 parts of 1-amino-8-hydroxynaphthalene-3,6- disulfonic acid are dissolved in 750 parts of water while adding sodium hydroxide solution to give a neutral solution. A solution of 148 parts of 3-(fl-chloroethylsulfonyD- phenyl-l-isocyanate in 325 parts of chlorobenzene of about 40 C. is added while stirring, and stirring is continued at a pH-value of 6-7 until practically all the 1- amino-8-hydroxynaphthalene 3,6-disulfonic acid has reacted. The chlorobenzene is then removed from the mixture by distillation in vacuo, the solution clarified at 40-50" C. by filtration and then cooled to 10-15 C. 121 parts of 33% sodium hydroxide solution are added, and the batch is stirred for minutes at 10-15 C. Subsequently the pH-value of the solution is adjusted to 5.8-6.3 by means of hydrochloric acid, 130 parts of sodium thiosulfate containing crystal water are introduced at 70-75 C., the pH-value being maintained by dropwise addition of glacial acetic acid. The reaction mixture is stirred at 70-75 C. for another 3 hours approximately, and then cooled to room temperature. By addition of sodium chloride the coupling component of the fol owing formula l NaO S-Q so Na so on CH s soN 3 3 T- 2 3 a is separated. The precipitate is filtered with suction and washed with a dilute aqueous sodium chloride solution.

(b) The moist filter residue obtained in this manner is mixed by stirring with 2,000 parts of water and 500 parts of ice and combined with the diazonium salt of 111.5 parts of Z-aminonaphthalene-l-sulfonic acid. The coupling mixture is neutralized by means of sodium carbonate solution and the coupling is allowed to terminate at 10-20 C. and at a pH-value of 6-7. The dyestuff, which in the form of the free acid corresponds to the following formula 28 is salted out with sodium chloride, filtered with suction, washed with a dilute aqueous sodium chloride solution and dried. It dyes and prints cotton clear, bluish red shades which are distinguished by good properties of wet fastness and, in particular, by a good fastness to bathing water containing chlorine.

Example 26 When using in Example 25 (b) instead of 111.5 parts of Z-aminonaphthalene l-sulfonic acid 151.5 parts of 2- aminonaphthalene 1,5-disulfonic acid and proceeding further as described in said example, there is obtained a dyestuff which in the form of the free acid corresponds to the following formula SIOaH H? 1?HCONH N=N HOS i SO H S O OH CH S 8011 3 V 3 2' 2- I- 3 SIOQH It dyes cotton bluish red shades distinguished by good properties of wet fastness, in particular by a good fastness to bathing water containing chlorine.

Example 27 (a) 217 parts of 2-amino 5-sulfobenzene-carboxylic acid are dissolved in 2,000 parts of water while adding concentrated sodium hydroxide solution to give a neutral solution and the whole is poured while stirring onto 2,000 parts of ice and 240 parts of 37% hydrochloric acid. Subsequently, the amino component is diazotized at 0-5 C. by treatment with 173 parts of 40% sodium nitrite solution, about 30 minutes after the last addition of nitrite the slight excess of nitrite is destroyed by means of amidosulfonic acid and the excess acid is neutralized by dropwise addition of saturated aqueous sodium carbonate solution. Then the solution of the coupling component obtained according to Example 19(a) from 319 parts of l-amino 8-hydroxynaphthalene 3,6-disulfonic acid and 296 parts of 3-(fl-chloroethylsulfonyl)-phenyl l-isocyanate and which is free from chlorobenzene is added, and the mixture is stirred at a pH-value of 6.5-7.0 until the coupling is complete.

The batch is then diluted with water to 19,000 parts by volume, filtered and to the filtrate obtained 3,800 parts of sodium chloride are slowly added. The precipitated dyestuff which in the form of the free acid corresponds to the following formula I 11035- SOaH SOi-GHi-OHa-Cl is filtered with suction, washed with dilute aqueous sodium chloride solution and dried at 60 C. in vacuo. It yields brilliant red dyeings and prints on cotton which are fast to wetting.

(b) 79.3 parts of the dyestulf of the formula given in paragraph (a) are stirred into 2,000 parts of water, 25 parts of copper sulfate containing crystal water are added, and the pH-value is adjusted to 5.0-5.5 by means of concentrated sodium carbonate solution. The mixture is stirred for 2 hours at 50-60 C., sodium chloride is added at room temperature, the precipitated dyestufi is filtered with suction, washed with an aqueous sodium chloride solution and the filter residue dried. The copper complex dyestuif obtained produces clear, reddish violet dyeings and prints on cotton.

(c) 79.3 parts of the dyestulf of the formula given in paragraph (a) are stirred into 1,000 parts of water, 25 parts of chromium alum are added, and the pH-value is adjusted to 5.5-6.0 by means of concentrated sodium carbonate solution. The mixture is then heated at this pH-value for 8 hours to 90-95" C., while stirring, su sequently the solution is clarified at room temperature by filtration, and the 1:2-chromium complex dyestuif formed is isolated by spray-drying. It yields bluish violet prints on cotton.

Example 28 is filtered with suction, washed with sodium chloride solution and dried. It yields blue dyeings and prints on cotton.

Example 29 When using in Example 8 instead of 12.5 parts of copper sulfate 14.1 parts of nickel sulfate containing crystal water and proceeding further as described in said example, there is obtained a metal complex dyestuff which in the form of the free acid corresponds to the following formula Ni o 17111 CH-NH o1 -N=N H038 SOaH SO:lCHr-CHz-Cl son:

The product dyes cotton reddish violet shades.

We claim: 1. Azo-dyestuff of the formula (SOaH)n wherein D represents (a) benzene or benzene substituted by 1 to 3 members selected from the group consisting of chlorine, lower alkyl, lower alkoxy, hydroxy, nitro, acetylamino, carboxylic acid, carboxylic acid N-sulfophenylamide and sulfonic acid amide,

(b) benzene sulfonic acid, benzene disulfonic acid or benzene sulfonic acid substituted by 1 or 2 members selected from the group consisting of chlorine, lower alkyl, lower alkoxy, hydroxy, carboxylic acid, tri- 5 fiuoromethyl, nitro, acetylamino and 2,4-dichlorotriazinyl-6-amin0,

(c) naphthalene substituted by 1 to 3 sulfonic acid groups, hydroxynaphthalene sulfonic acid or hydroxynaphthalene disulfonic acid,

(d) azo-benzene sulfonic acid, azobenzene disulfonic SOWCH2-CHICI 3. The azo-dyestutf of the formula 4. The azo-dyestufi of the formula SOaH HO 5. The azo-dyestufl of the formula 

